Separating fluorine compounds



Patented Sept. 11, 1945 SEPARATING FLUORINE COMPOUNDS Anthony F. Benning, Woodstown, N. 3., and

Joseph D. Park,

Kinetic Chemicals, Inc.,

Wilmington,

Del., assignora to Wilmington, DeL, a

corporation ofDelaware- No Drawing. Application September Serial No. 501,151

2 Claims.

,A. This invention relates to the separation of the elements of a composition which is produced by a prior process. By the process of U. S. Application Serial No. 475,526, filed on February 11, l943, by F'. B. Downing, A. F. Benning and R. C. McHarness, there is produced compounds identilled by their respective formulas as C4FB (called octafluorocyclobutane) andCzl-IClF'r (called tetrafluorochloroethane). Bythe process of Example XXII of that application, which is re peated hereinafter for purposes of completeness, there is produced a mixture containing these two compounds. This mixture is azeotropic. The mixture is useful as a refrigerant, as a solvent, and for other purposes where the use of the mixture is satisfactory, but the two compounds have higher utilityas individuals than they do as a mixture. The value of the compounds is such with a mineral oil. A more detailed description of the invention is found hereinafter.

D. In the following examples parts are by weight unless otherwise specified. Example I corresponds to Example m of the application of.

Downing, Benning and McHarness, Serial No. 475,526. The invention is not limited to mixtures produced in this way but may be satisfactorily employed wherever an azeotropic mixture of the type involved is found.

Example I w Ser. No. 475,526, 'a large amount of material boiling above 40 C. was obtained. The following are among the compounds which were isolated and identified. Some of their physical constants that a separation, to be economically satisfactory, are given.

. Moi. wt. No. Compound B.pt. l Density in!) cm. Found c. norm-.01..-- 21 186.6 ms nomoi to nu ma 3. HOsFuOl... 77 mg] 3 Heir" 101 5.1.... HCIFH 123 6"... HCrFuC 143 Hour m Mel. wt. No. Compound B. pt. Vupordeusity nD Colo. Pound 'c. I v or 01.... -m 5.1 aura...

. oiri -s sag nsure mfilssumes PV-RTwhicli to: compounds mm: type gives a M. mu 04% must be substantially quantitative. The problem yielded to no ready solution. and all the methods of separation attempted were technically or eco-' nomically unsatisfactory excepting that which isdesci'ibed herein. 1

B. It is anfobiect of this invention to overcome the dlfllculties inherent in the separation of the members of the azeot'ropic mixture containing C41: and CaHC1F4. a

C. The objects of the invention are accomplished, generally speaking, by extracting the -"point of 4 C.

Several constant boiling mixtures were also found in the pyrolysis material; one of them boiled at about 12 C. and contained about vol. of C2HCiF4 and another component boiling at 4 C. and had a molecular weight of about 202; another boiled at about 8 to 9 C. and contained about vol. CH'ClzF; another had s boiling Example II The mixture boiling at l2' C., obtained by azeotropic mixture containing CiFl and CIHClFi 6 the pyrolysis of CHCH": as described in Exampic I, was extracted repeatedly with lubricating used in the extraction: examples '0! them are oil having a naphthenic base and the following the oils having thespeciilcations:

cm-Facteflsmfi Gravity A. P. I./60 F 22 to 25.5 Gravity A. P. I./60 F 23.5-23 Viscosity index to 50 Pour point A. S. T. M 40 F. Pour polnt'A. S. T. M Not higher than 70' F. viscesty index +2 Intermediate fractions of mineral oil containing The extraction was carried out in a 4 lb. cvlina mixture of naphthenic and parafllnic bases may der fltted with a sight glass and a valve. The also be used. cylinder was evacuated, chilled in a COz-acetone E. The process may be continuous or in batches. bath to a temperature below -12 0., about 1.5 It continuous, it may be with parallel now or lbs. of the lubricating oil was admitted to the countercurrent. Lower and higher temperatures cylinder at a temperature below 12 C. and than those given may be used for carrying out about one pound of the 12 C. fraction was the extraction if in the opinion of the chemist added. The cylinder was removed from the bath 15 an advantage is obtained. and allowed to warm to room temperature. It F. As many apparently widely difierent emwas intermittently agitated. After several hours bodlments of this invention may be made witha raflinate (lower layer) was separated from the out departing from the spirit and scope thereoil phase. The CzHC1F4 was removed from the of, it is to be understood that we do not limit oil phase by boiling. The oil was used for a secourselves to the specific embodiments thereof exond extraction of the rafllnate and the cycle was cept as defined in the appended claims. repeated six times. The extract removed from We claim: the oil had a boiling point of -10 C. and a l. The process of separating members of an molecular weight of 140.2 by the vapor density azeotropic mixture comprising 04F; and CzHClF4 method. Theoretical molecular weight is 136.5 which comprises extracting the mixture in the for C2HClF4. Chlorination of the product yielded liquid phase with a mineral oil having a napha compound having a boiling point of +4? C. thenic base, a sp. g. A. P. I./60 F. from 22-285, and a molecular weight of 1'75 indicating the a viscosity index ranging from 0-50, and a pour presenceof C2HC1F4. point not higher than 70 F.

The raffinate after eight extractions gave up 2. The process of separating members of an a product with a boiling point of 4 to -5 C.,' azeotropic mixture comprising C4Fs and CzHClF4 a melting point 01' 48 C., and a molecular which comprises extracting the mixture in the weight of 202. The boiling point of C4Fa prepared liquid phase with a mineral oil having a naphby other methods is 5 C. and the calculated .thenic base, :3. sp. g. A. P. I./60 F. of about molecular weight is 202. Mixed melting points 5 23.5-23, a viscosity index of about +2 and a pour and comparison with authenticated samples oi point of about F. CQF! obtained otherwise showed the compounds ANTHONY F. BENNING. to be identical. JOSEPH D. PARK.

Other naphthenic base mineral oils may be 

